Process for the preparation of monocyclic ketones and their alkyl derivatives having more than nine ring members



Patented Feb. 19, 1929.

UNITED STA LEOPOLD RUZICKA, OF GENEVA,

TES

SWITZERLAND, ASSIGNOB TO' Mt NAEF & C0, OF

GENEVA, SWITZERLANDQA COM'PANY OF SWITZERLAND.

PROCESSFOR THE PREPARATION OF MONOCYCLIC KETONES AND THEIR ALKYL DE- RIVATIVES HAVING MORE THAN NINE R11? G MEMBERS.

No Drawing. A'pplication filed November 19,

In the prior application, Serial No. 36,049, filed June 9, 1925, now Patent No. 1,673,093, there is described a process for the formation of monocyclic ketones having more than nine ring members, according to which normal dicarboxylic acids having more than ten carbon atoms in a normal chain are subjected to the usual methods for preparting ketones. It has been found advantageous to use thorium for these methods. g

It has since been discovered that according to these methods the alkyl derivatives of the above mentioned ketones can be obtained. This discovery forms the subject of the present invention. ,p

According to the present invention alkyl derivatives of monocyclic ketones having more than nine ring members are prepared by starting from the alkyl derivatives of the dicarboxylic acids having more than ten carbon atoms in a normal chain. The use of metals or compounds of metals belonging to the fourth group of the periodic system for instance thorium has also been found advantageous.

It is also advantageous to use a mixture of these metals or of a mixture of two or more metals of the third and fourth groups of the boXylic acids or their alkyl derivatives, which 1926, Serial no. 149,542, and infSwitzerland December 15, 1925. a

alkyl derivatives or such as they are obtained vincertain technical processes or from natural products, give according to the present invention mixtures of the ketones or their alkyl derivatives Which, in this form, can also be employed in practice. I

For obtaining the mentioned monocyclic ketonesit is also possible to heat directly the acids or theacid anhydrides alone or in presence of metals or metal compounds to a coinparatively high temperature, instead of first transforming the corresponding dicarboxylic acids into salts. In this'case the use of metals of the fourth group of the periodic system iS also advantageous. I

The ket'ones and their alkyl derivatives obtained by the described process can be used as perfumes or as primary materials for the preparation of other technically important compounds. Y

Example 1.

a vacuum, up to 300 to 500 degrees centigrade and the distillate obtained therefrom is Worked up by fractional distillation. The fractions distilling at from 100 to 150 C. at a pressure of 0.5 mm. are then treated with semicarbazide or other reagent usually'employed for isolating the ketones.

The formation of the 3-methyl-cyclopentadecanone can be represented'by the follo-ware prepared from the pure acids, or their ing equation cum-coo 0112K o1non ThdCIRP'Cfi OO+Tl1O2+2CO2 (CH2)11COO 2 Example 3-methyl-tetradecane-1.14-dicarboxylic acid is heated up to above 300 to 500 degrees centigrade and towards the end of the reaction preferably in a vacuum -with thorium hydroxide in a quantity which does not suflice for completely converting the acid into the normal salt. The product obtained is treated accordingto the method described in Ex ample 1.

E sample 3.

A mixture of thorium and cerium salts of 4.-methyl-tetradecane-1.14-dicarboxylic acid is heated and worked up as described in Example 1. The 4-methyl-cyclopentadecanone obtained boils at about 125 C. (at 0.3 111111.), gives a semicarbazone melting at about 100 C. and has a smell practically corresponding to that of natural. musk and can therefore be used perfume and for preparing other interesting technical compounds.

Ewample 4.

1-methyl-tetradecane-LM-dicarboxylic a cid is heated at about 300 to 500 C. and towards the end of the reaction preferably in a vacuuin with thorium oxide. The product 0btaiued is worked up as described in EX- ample 3.

Example 5.

The thorium salt of octadecane-l.18-dicarboxylic acid is heated preferably 111 a Vacuum to about 300 to 500 C. and the resultins; distillate is worked up by fractional distillation. The fraction distilling at from 1 10 to 180 C. (at 0.3 mm.) is then treated With semicarbazide or another reagent usually employed for isolating the ketones. The

cyclononadecanone in a pure state can in this manner be isolated by treating the semicarbazone purified by crystallization from alcohol and melting at 184i C. This ketone boils at 100 C. (at 0.3 111111.), melts at '?2 C. and 112 s a smell which nearly corresponds to that oi civetone. it can tiierei ore be used as a perfume and as a primary material for pre paring other interesting 1 technical con pounds; by oxidizing the cyclouonadecanone with chromic acid heptadeczuie-l'.1T -dicarboxylic acid is formed.

I claim:

1. A process for the preparation of alkyl derivatives of monocyclic lrotones having more than nine ring members comprising heatin thorium .s of alk l derivatives of 1 n J u pot tnylei'ie dicarboizyhc acids, hav ng I more than ten carbon atoms in a normal chain the carlmxylic acid groups being linked to the end carbons thereof. 7

2. A process for the preparation 01" alkyl derivatives of monocyclic ketones having more than nine members comprising heating a mixture of thorium salts and cerium oi allryl derivatives of polymethylene dicarboxylic acids having more than ten carbon atoms in a normal chain, the

carboxylic acid groups being linked to the end carbons thereof.

in testimony whereof I affix my signature.

LEOPOLD RUZICKA. 

